Thin sheet of phosphor embedded glass and method of preparing



Oct. 2l, 1958 E. P. ETZEL ETAL 2,857,541

' THIN SHEET oF PHosPHoR EMBEDDED GLASS AND METHOD OF PREPARING Filed March 29. 1954 65e/MD @Mss ro A Pawnee INVENTORS. fac-:EWE F? Erzsz. .ma 07m/6 ArW/f/ a/ WE/ United States Patent THIN SHEET OF PHOSPHR EMBEDDED GLASS AND METHOD F PREPARING Eugene P. Etzel, Upper Montclair, and Chung Kwai Lui Wei, Bloomfield, N. J., assignors to Westinghouse Electric Corporation, East Pittsburgh, Pa., a corporation of Pennsylvania Application March 29, 1954, Serial No. 419,232

1 Claim. (Cl. 313-108) This invention relates to thin sheets of phosphor or luminescent material embedded glass and to methods of making same, and more particularly, to electroluminescent cells which incorporate thin sheets of phosphor embedded glass as a phosphor-dielectric.

Heretofore, electroluminescent cells have been made as described in Patent No. 2,566,349 to Mager, or as described in New Phenomenon of Electrophotoluminescence by G. Destriau, Philosophical Magazine, October 1947,

vol. 38, pp. 700-737.

In such electroluminescent cells, or electroluminescent lamps as they are also called, the phosphor material is normally embedded throughout a thin sheet of plasticdielectric which dielectric preferably has as high a dielectric constant as possible and which dielectric is made as thin as practicable in order to increase the electric field between the cell electrodes. A plastic dielectric has several disadvantages. Many of the plastic dielectrics are thermoplastic in nature and tend to soften at relatively low temperatures, e. g. 70 C. to 100 C. in the case of cellulose acetate. Since it is sometimes desirable to operate these electroluminescent cells at temperatures within or above the softening range of the plastic-dielectric, it is necessary to provide a backing plate of glass or other suitable material for the cell in order to give the cell sucient rigidity so that it can support even its own weight.

An even greater disadvantage to the use of a plastic as the dielectric material is the tendency of plastics to slowly absorb moisture from the air. This moisture absorbing characteristic lowers the dielectric strength thereby decreasing the brightness of the cell and causing eventual premature breakdown of the cell. q

To overcome these water absorbing and softening characteristics of plastics, it has been proposed to replace the plastic dielectric with a glass dielectric, since glass can be made relatively impervious to atmospheric Water vapor, thereby enabling the cell to retain its brightness and preventing a premature breakdown of the dielectric. In addition the cell can be operated at elevated temperatures.

Various means are known for forming sheets of impregnated glass. In one of these methods ground glass and the impregnating material, in this case the phosphor, are deposited in nely divided form on a plate to the desired thickness and the glass is red to cause it to fuze. In another method, the phosphor and powdered glass are suspended in a liquid medium such as water and allowed to slowly settle onto a plate. The liquid medium is then drained olf and the layer of powdered glass and phosphor are then fired to cause the glass to fuze.

In these methods of the prior art for fabricating the thin sheets of phosphor-glass dielectric, the results have been very unsatisfactory due to the tendency of the glass to have many air bubbles and discontinuities. Such air bubbles and discontinuities cannot be tolerated in an electroluminescent cell for they constitute small areas in which the total dielectric between the cell electrodes is decreased, thereby causing the cell brightness to vary and forming Patented Oct. 21, 1958 ice weak points at which breakdown, or arcingbetween electrodes, will occur. l

It is the general object of the invention to avoid and overcome the foregoing and other diiculties of and objections to prior art practices by the provision of a method of forming a thin sheet of phosphor embedded glass.

It is a further object to provide a thin sheet of phosphor embedded glass wherein there are substantially no discontinuities and/ or air bubbles in the glass dielectric.

It is another object to provide a method of makingan electroluminescent cell wherein the dielectric consists of a glass.

It is still another object to provide an electroluminescent cell wherein the dielectric is a glass.

It is yet another object to provide an electroluminesdered glass, pouring the slurry intofa plaster mold tov form a green plaque, and firingthe green plaque to fuze the glass. This results in a thin sheet of phosphory embedded glass which has substantially no discontinuities or air bubbles. l

For a better understanding of the invention reference should be made to the accompanying drawing wherein:

Fig. l is a perspective view of an electroluminescent cell embodying the thin sheet of phosphor embedded glass of this invention.

Fig. 2 is a flow diagram illustrating the method used in fabricating the thin, sheet of phosphor embedded glass of this invention.

Although the principles of this invention are broadly applicable to thin sheets of phosphor impregnated glass and to methods of making same, .the inventionhas particular application in electroluminescent cells and hence has been so illustrated and will be so described.

With specific reference to the form of the invention illustrated in the drawing,` the numeral 10 indicatesv generally an electroluminescent cell comprising a irst electrode 12, which may consist of a thin transparent sheet of tin oxide, if desired. O'ver'the rst electrode there is positioned a thin sheet of phosphor nembedded glass 14 and a second electrode 16 is-placed over the phosphorglass dielectric. This second electrode may consist of a thin sheet of vaporized aluminum or silveror may consist of a thin transparent sheet of tin oxide if itis desired that both electrodes be transparent. Thin copper ribbons 18 may be soldered or otherwise electrically connected to the electrodes, if desired,` to facilitate making electrical contact to the cell electrodes. 1

The glass in which the .electroluminescent phosphor is embedded and which serves as the dielectric must meet several requirements: First, the glass ispreferably transparent in order to pass the light generated by the phosphor, but a translucent glass will be satisfactory if Vsome eciency is to be sacriced. Second, when melted the glass should not take the electroluminescent phosphor into solution nor chemically attack nor combinewith the phosphor. Forexample, if a zinc sulfide phosphor is used, it is desirable not to have any lead, nickel or copper present in the glass or it is apt to deleteriously affect the phosphor. Of course, if other phosphors were to be used and would not react with these heretofore mentioned glass components, it would be satisfactory `to Y examplethe tellurite glass may have the;.composition--- hasea dielectric-constant...of about,.27.5. Since 'mostiv glasses-and plasticsx-.havea dielectrioonstant.- between about 4 to 7..` and.e1ectroluminescent-cell-.brightness.is pro-L portional .-to :dielectric:.constant,.--the advantages realized through. themse .of lead telluriterglassean. readily be appreciatedynamely a vgreat:V increase in Mcell...brightness.A

Third, theglassshould-have'a low viscosity whenmelted in :order .to enable rit-to .flow.togetheneffectivelyy about;v

the phosphor and form a thin even sheet. For example, a viscosity. offrom1,45 10.165. dyinescrn.A at .7004 C. is

suitable. This desired viscosityA is notintended as a limitation,-but is Aonly....given..as 1an. indication: of what will produce the ,.best type-thin.. phosphor-glass. sheet;Y

'There desirably is present .in the glass'a flux. to facili-Y tate. glass fusion, :examplesbeing ,sodium .oxide, fcalcium oxide,. magnesium.oxide, .lith-ium... oxideqyor .potassium oxide( or other suitable .uxingagentsrn There should. also: be presentin theglass a stabilizingkagent such as barium.. oxide, aluminum oxide, .silicon dioxide.. or .calcium foxide,

or other .suitable .stabilizing .agent rwhich.V will .promote hardness in the glass'..andkeep..it .from .being v.water-- soluble.

The number of different glasses which Will .meet these foregoing requirements is very largeand.anymanfskilled in the art can. readily name .several dozen diierent suit-.

able .glasses without `eve'n,referring1y to reference (texts.v Examples of satisfactory glasses. are asfollows:

In preparing the thin sheet"ofphosphorglass of 'this invention, the glass comprising theA dielectric is first ground in an agate mortar or` pulverized `Vby other 'conventional' mixing means 1 such Vas^hamrnermi1ling for' "about 30 minutes'or until the powderedfglass Willpass 'a 200 mesh sieve 'and'catch on a 325 mesh'sieve `(U. S. Standard'y sieve series).V This degree of neness isV in notway critical, but represents What'is considered to be a generally satisfactory degree of 'pulverization Phosphor or luminescent material" is then'mixed iwith the. glass in amount'of about 1/2% by'weight'of 'the 'glassjalthough the'phosphor may varyfrom aboutO.01% to 4%'byweight of the glass. The `poWderedgla'ss andphosphor are then `thoroughlymixecv by stirring, shaking, yvibrating or other conventional mixing techniques'.

The' mixed powdered glassand-phosphor are then incorporated in a slurryby Vadding Water in amounts which mayivary from Vabout 3% to 5 times theweight ofthe phosphor and glass.- An electrolyte .isvalso added tothe slurry in amounts which may vary from about r0.5 gram 4 to 2 grams of electrolyte per liter of slurry, although the amounts of electrolyte which may be added may vary greatly over wide limits depending upon the choice of the electrolyte and the strength of the electrolyte used. The purpose of the electrolyte isto deocculate the glass and-phosphor particles by giving them a slight -charge so t that they will vrepel one another and-be evenly dispersed.

Although it is not necessary, it is desirable to add a binder to the slurry in amounts- `which may vVary from l traces V(e. g., .01%) to about 3% .by Weightof the slurry. This tends' to 'lend adhesiveness, orV so-called green strength of the particles for one another When they are formed-.into a green plaque, as '.hereinafterexplained.. Most any commercially available binder issuitable but as an example any Vof theV alginates, glucose or dextrine may be used. By way of explanation alginates are Water soluble. .salts of alginic..acidsxtractedrfrom.a giant kelp plant of the. PaciiioOcean.:

The:slurry is thoroughly mixed .andthen poured into i a moisture-absorbingmold1such as..onek of plaster. of

Paris, which mold hasthe desiredgeneral shape of the l thinV sheet. of .phosphor-glass.: The .mold of `plaster .of Paris or the likewithdrawsthe-Water from the slurryA leavingY a .green plaque...which is. quitecompact due to packing effect experienced as the Water is drawn by the plaster of Paris mold. A mold is desirablyformed in.

multiple partsv so. that one half of the. mold may be lifted after `the green plaqueis formed, .Without disturbing the plaque.

The green plaqueis then .removed from the remaining Y halfOf thelmold without cracking .it by .means of thin spatulas which may be insertedunderthe green plaque to support it, or. by means vof a formed receptable which has vthe configuration of the green plaque. and in which receptacle theplaque maybe tired..A If such a formed receptacle is used, `4they upper portion of the .mold is re. moved andthe receptacle placed over the exposed` part of the green plaque. Theplaque. is then inverted and the remaining portion of the. plaster of Pasmold Withdrawn leaving the green plaque in the receptacle.. Y

It was `unexpected that the green plaque would have.. suicient body to enableit to hold together While in the green state before it was red, particularly When the plaque may have an area of perhaps .4 squareinches and a thickness of lonly about2 mm., for example.. It is easy to conceive of mak-ing a wetor moist ball of sand or powdered glass adhere Vtogether withoutcracking, but it was completely unexpected. .that vsuch-.a =very thinsheet of. material would adhere together .thegreen state Without developing:cracks or other discontinuities..

. The green .plaque in the.. receptacle, which receptacle may be platinum,..if desired,s thenplacedin the'ng s ovens. and. red in an atmosphere `suitable to the glass and the phosphorwat a temperature slightly above thesoftening temperature .of the glassuntilthe. glass is substantially fused .to itself and about thephosphorparticles which are evenly dispersed. therein. During thelring the organic binder, if one is used, Will carbonize and volatilize from the phosphor-glassgreen plaque. Since suchbinders Y normally substantially completely volatilize at. about 500'. C., substantially no organic .binder will remain in the .plaque when the glass `fuzes.

Informing. thegreen plaque from the slurry, the` plaqueA willshrink or compress about-3% from the volurneV ofthe plaster of Paris. mold.- When tired the green plaque will shrink about another 20%. Thus therplaster of Paris mold should havea volume`faboutf22% or: 24% greater. than .the-desired volume ofthe iiredphosphor embedded glass, although thegenera1v configuration' of Y the fired phosphor embedded glass iandfthe mold vvvill be substantially the same. H

As a speci-fic example,i10igrams of'vthekpowdered glass of Example'l may be mixed With 0.05 gram ofzinc sul-v ticlev phosphorT activated fby; y10.-.4zparts by Weightloffcopper.V

This powdered glass and phosphor are then thoroughly mixed and are incorporated into a slurry by adding about 40 grams of water to the phosphor-powdered glass mix and about 0.04 gram -of barium acetate or 0.06 gram of 3 normal ammonium hydroxide, lwhich mixture is agitated to form the slurry.

If desired, about 0.6 gram of tn'isopropanol amine salt of alginic acid may be added to the slurry as a binder.-

The slurry is then poured into a plaster of Paris mold, which as an example may have a square configuration 4 inches on a side and a thickness of 2.5 mm. The slurry is allowed to remain in the mold until the water is substantially withdrawn and the green plaquey becomes leather hard with a rin texture, which will take about 30 minutes, for example. The upper half of the plaster mold is then withdrawn, the plaque placed in a platinum receptable and the green plaque and receptacle placed in a firing oven and red in an air atmosphere for about 3 minutes at a temperature which is slightly above the softening temperature of the glass,which in the case of the vspecific example given may be about 690 C. 'I 'he fuzed plaque is then withdrawn from the tiring oven and allowed to slowly cool in air.

ln order to fabricate the electroluminescent cell as illustrated in Fig. 1, thin transparent conductive coatings may be applied to either side of the phosphor-dielectric thin sheet as described in Patent No. 2,522,531 to I. H. Mochel or as described in Patent No. 2,667,428 to Young et al. lf it is desired to make one of the electrodes opaque, this electrode may be applied as a thin coating or aluminum or silver by well known vacuum metallizing techniques. Connecting copper strips which facilitate electrical connection to -the cell may then be applied as described in Patent No. 2,628,299 to Gaiser.

If it is desired to provide the electroluminescent cell with a backing plate to increase its mechanical strength glass or other nonconductive material may be applied over one of the electrodes 4and axed to it by means of an adhesive such as a polymer resin containing the epoxide group o H C./ \0. i i i as the polymerizing unit. One such resin is manufactured by the Ciba Co. Inc. under the trademark Araldite- AN-l00. Other suitable adhesives could of course be used.

It will readily be understood that if lead tellurite glass `is te be used as the dielectric, which glass has a dielectric constant of about 25-30, the Zinc sulfide copper-activated phosphor as heretofore described is first provided with a thin protective coating such as silica by means as described in the heretofore mentioned Beese patent. It may be desirable to paint or otherwise protect the exposed sides of the glass not covered by the electrodes, although this is not necessary.

It will be recognized that the objects of the invention have been achieved by provision of a method of forming a thin sheet of phosphor-embedded glass in which there are substantially no discontinuities and/ or air bubbles and which sheet may be fabricated into an electroluminescent cell. This thin sheet may be used in applications where the sheet is exposed to atmospheric water vapor and there will be substantially no tendency to absorb this water Vapor. Also, the thin sheet of phosphor-glass may be operated at elevated temperatures, which may approach the softening temperature of the glass.

While in accordance with the patent statutes, one best known embodiment of the invention has been illustrated and described in detail, it is to be particularly understood that the invention is not limited thereto or thereby.

We claim:

An eleetroluminescent cell comprising two electrodes having a thin layer of phosphor embedded glass sandwiched therebetween, said glass being lead tellurite, and

said phosphor comprising multiple particles each sur-` rounded by a thin protective coating.

References Cited in the file of this patent UNITED STATES PATENTS v 2,049,765 Fischer Aug. 4, 1936 2,151,496 Beese Mar. 21, 1939 2,208,034 Korach et al July 10, 1940 2,314,824 Greene Mar. 23, 1943 2,508,901 Bellezza May 25, 1950 2,566,349 Mager Sept. 9, 1951 2,689,188 Hushley Sept. 14, 1954 OTHER REFERENCES Seare: Encyclopedia of Ceramics Ind., published by Ernest Benn Ltd. London, 1930, vol. 3, p. 171. 

